Synlett 2013; 24(12): 1597-1598
DOI: 10.1055/s-0033-1339302
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© Georg Thieme Verlag Stuttgart · New York

(1R,2R)-Diaminocyclohexane

Paweł Tokarz
University of Łódź, Department of Organic Chemistry, Tamka 12, 91-403 Łódź, Poland   Email: paweltokarz.chem@gmail.com
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Further Information

Publication History

Publication Date:
26 June 2013 (online)

Introduction

trans-1,2-Diaminocyclohexane (1), denoted as trans-DACH, is a chiral molecule with C 2 symmetry. It was synthesized for the first time in 1926 from hexahydrophthalic acid by Wieland.[1] A convenient way for the resolution of the enantiomers was introduced by Whitney in 1980.[2] An aqueous solution of racemic trans-DACH and enantiomerically pure l-(–)-tartaric acid was treated with glacial acetic acid and the resulting white precipitate of enantiomerically pure (1R,2R)-diaminocyclohexane tartarate was subsequently treated with an aqueous solution of KOH yielding 1 (Scheme [1]). Recently, it was demonstrated that the second enantiomer can be recovered from the resulting filtrate with another portion of l-(–)-tartaric acid.[3]

In the early 1990s, Jacobsen and co-workers published two subsequent papers on the enantioselective oxidation of olefins catalyzed by an imine complex derived from (1R,2R)-diaminocyclohexane.[4] Since then, the interest in DACH-based compounds in chiral synthesis has been growing. Although many derivatives of the compound have been applied in chiral catalysis, recent years brought catalytic and synthetic applications of trans-DACH itself.

Zoom Image
Scheme 1
 
  • References and Notes

  • 1 Wieland H, Schlichtung O, Langsdorf WV. Z. Phys. Chem. 1926; 161: 74
    • 2a Whitney TA. U.S. Patent 4 085138, 1978
    • 2b Whitney TA. J. Org. Chem. 1980; 45: 4214
  • 3 Mucha P, Mlostoń G, Jasiński M, Linden A, Heimgartner H. Tetrahedron: Asymmetry 2008; 19: 1600
    • 4a Zhang W, Loebach JL, Wilson SR, Jacobsen EN. J. Am. Chem. Soc. 1990; 112: 2801
    • 4b Jacobsen EN, Zhang W, Muci AR, Ecker JR, Deng L. J. Am. Chem. Soc. 1991; 113: 7063
  • 5 Liu Y, Wang J, Sun Q, Li R. Tetrahedron Lett. 2012; 52: 3584
  • 6 Fabio RD et al.. J. Med. Chem. 2008; 51: 7370
  • 7 Carril M, SanMartin R, Domínguez E, Tellitu I. Chem.–Eur. J. 2007; 13: 5100
  • 8 Wang J, Qi C, Ge Z, Cheng T, Li R. Chem. Commun. 2010; 46: 2124
  • 9 Skowronek P, Gawroński J. Org. Lett. 2008; 21: 4755
  • 10 Tanaka K, Shimoura R, Caira MR. Tetrahedron Lett. 2012; 51: 449
  • 11 Tanaka K, Tsuchitani T, Fukuda N, Masumoto A, Arakawa R. Tetrahedron: Asymmetry 2012; 23: 205
  • 12 Rivera A, Quiroga D, Jiménez-Cruz L, Fejfarová K, Dušek M. Tetrahedron Lett. 2012; 53: 345
  • 13 Kwiatkowski P, Mucha P, Mlostoń G, Jurczak J. Synlett 2009; 1757
  • 14 Hou W, Zheng B, Chen J, Peng Y. Org. Lett. 2012; 14: 2378
  • 15 Kapoor I, Schön EM, Bachl J, Kühbeck D, Cativiela D, Saha S, Banerjee R, Roelens S, Marrero-Tellado JJ, Díaz DíazD. Soft Matter 2012; 8: 3446 . The image of the gel was provided and used under permission from Ms. Eva Maria Schön who is thanked for fruitful discussions